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US4582693A
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Synthesis of silica molecular sieves using synthesis directing organic dyes
Assignee: Standard Oil Co
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Filing: 1984-11-16
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Granted: 1986-04-15
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Expires: 2004-11-16
Abstract
Abstract A method is disclosed for making a silica molecular sieve comprising: (A) providing a mixture comprising: water; an oxide, hydroxide or alkoxide of silicon; a mineralizing agent; and a synthesis directing nitrogen containing organic dye; and (B) maintaining said mixture at a temperature of about 80° C. to about 300° C. for an effective period of time to provide said silica molecular sieve.
Inventors
- 👤 Michael J. Desmond
- 👤 Frederick A. Pesa
- 👤 Janie K. Currie
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 06:39
CPC Classifications
C; C01; C01B; C01B33/00; C01B33/113; C01B33/12; C01B33/18; B; B01; B01J; B01J29/00; B01J29/03; B01J29/035; C01P; C01P2002/00; C01P2002/20; C01P2002/22; C01P2002/70; C01P2002/72; C01P2002/74; C01P2006/00; C01P2006/80
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
384 words
A method for making a silica molecular sieve using a nitrogen-containing organic dye, said silica molecular sieve being represented in terms of mole ratios of oxides by the formula aAO.sub.n/2 :xM.sub.2 O:yAl.sub.2 O.sub.3 :100SiO.sub.2 :bH.sub.2 O wherein A is the cation of said organic dye; M is an alkali metal; a is from zero to about 2; n is the cationic charge of A; b is from about 20 to about 90; x is from about about zero to about 15; and y is from zero to about 2; said process comprising the following steps: (A) providing a mixture comprising: water; an oxide of silicon source; a mineralizing agent selected from the group consisting of alkali and alkaline earth metal compounds; and said nitrogen containing organic dye; the mole ratio of OH - to Si being in the range of about 0.1 to about 10, the mole ratio of Si to mineralizing agent being in the range of about 0.1 to about 50, and the mole ratio of Si to organic dye being in the range of about 5 to about 50; said organic dye being a substituted benzylidene compound represented by the formula (I) ##STR3## wherein N 1 has a charge of +1 or a neutral charge; N 2 has a charge of +1 or a neutral charge; x is zero when N 1 has a neutral charge, and is 1 when N 1 has a +1 charge; y is zero when N 2 has a neutral charge, and is 1 when N 2 has a +1 charge; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently hydrogen or alkyl groups of 1 to about 10 carbon atoms; z is 1+x+y; Q is an anion of charge c; and d is z/c; or said organic dye being the salt of a cation of the formula(II) ##STR4## wherein R 9 and R 10 are independently hydrocarbon groups of from 1 to about 10 carbon atoms; or said organic dye being selected from the group consisting of methylene blue, methylene green or alcian blue; and (B) maintaining said mixture at a temperature of about 80° C. to about 300° C. for an effective period of time to provide said silica molecular sieve.
Claim 2
Independent Claim
384 words
A method for making a silica molecular sieve using a nitrogen-containing organic dye, said silica molecular sieve being represented in terms of mole ratios of oxides by the formula aAO.sub.n/2 :xM.sub.2 O:yAl.sub.2 O.sub.3 :100SiO.sub.2 :bH.sub.2 O wherein A is the cation of said organic dye; M is an alkali metal; a is from zero to about 2; n is the cationic charge of A; b is from about 20 to about 90; x is from about about zero to about 15; and y is from zero to about 2; said process comprising the following steps: (A) providing a mixture comprising: water; an oxide of silicon source; a mineralizing agent selected from the group consisting of alkali and alkaline earth metal compounds; and said nitrogen containing organic dye; the mole ratio of OH - to Si being in the range of about 0.1 to about 10, the mole ratio of Si to mineralizing agent being in the range of about 0.1 to about 50, and the mole ratio of Si to organic dye being in the range of about 5 to about 50; said organic dye being a substituted benzylidene compound represented by the formula (I) ##STR3## wherein N 1 has a charge of +1 or a neutral charge; N 2 has a charge of +1 or a neutral charge; x is zero when N 1 has a neutral charge, and is 1 when N 1 has a +1 charge; y is zero when N 2 has a neutral charge, and is 1 when N 2 has a +1 charge; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently hydrogen or alkyl groups of 1 to about 10 carbon atoms; z is 1+x+y; Q is an anion of charge c; and d is z/c; or said organic dye being the salt of a cation of the formula(II) ##STR4## wherein R 9 and R 10 are independently hydrocarbon groups of from 1 to about 10 carbon atoms; or said organic dye being selected from the group consisting of methylene blue, methylene green or alcian blue; and (B) maintaining said mixture at a temperature of about 80° C. to about 300° C. for an effective period of time to provide said silica molecular sieve.
Claim 3
Dependent Claim
35 words
The method of claim 1 wherein A is the cation of methyl viologen, ethyl viologen, benzyl viologen, betaine viologen, methyl green, ethyl green, methylene green, methylene blue, methyl violet, methyl violet 2B or alcian blue.
Claim 4
Dependent Claim
11 words
The method of claim 1 wherein M is Na or K.
Claim 5
Dependent Claim
9 words
The method of claim 1 wherein M is Na.
Claim 6
Dependent Claim
13 words
The method of claim 1 wherein a is from zero to about 1.
Claim 7
Dependent Claim
14 words
The method of claim 1 wherein b is from about 30 to about 80.
Claim 8
Dependent Claim
14 words
The method of claim 1 wherein x is from about zero to about 10.
Claim 9
Dependent Claim
13 words
The method of claim 1 wherein y is from zero to about 0.5.
Claim 10
Dependent Claim
15 words
The method of claim 1 wherein n is in the range of 1 to 4.
Claim 11
Dependent Claim
103 words
The method of claim 1 wherein said organic dye is said substituted benzylidene compound (I), said salt of a cation of the formula (II) of said alcian blue, said period of time for step (B) is in the range of from about one to about fifteen days, the X-ray diffraction pattern for said silica molecular sieve shows at least the following significant lines: ______________________________________
Interplanar Relative
Spacing d(A) Intensity
______________________________________
15.65 ± 0.2 v.s.
7.78 ± 0.1 w.
5.18 ± 0.06 m.
3.64 ± 0.04 w.-m.
3.56 ± 0.04 w.-m.
3.44 ± 0.04 s.-v.s.
3.31 ± 0.03 m.-s.
3.15 ± 0.03 m.-s.
______________________________________
Claim 12
Dependent Claim
71 words
The method of claim 1 wherein said organic dye is methylene blue or methylene green, the X-ray diffraction pattern for said silica molecular sieve shows at least the following significant lines: ______________________________________
Interplanar Relative
Spacing d(A) Intensity
______________________________________
18.5 ± 0.3 s.
13.7 ± 0.2 m.
10.8 ± 0.2 m.
4.10 ± 0.06 v.s.
3.68 ± 0.08 m.
3.49 ± 0.05 s.
2.49 ± 0.02 m.
1.84 ± 0.01 m.
______________________________________
Claim 13
Dependent Claim
124 words
The method of claim 1 wherein said organic dye is said substituted benzylidene compound (I), said salt of a cation of the formula (II) or said alcian blue, said period of time for step (B) ranging from about 4 hours to about 30 days, the X-ray diffraction pattern for said silica molecular sieve shows at least the following significant lines: ______________________________________
Interplanar Relative
Spacing d(A) Intensity
______________________________________
20.1 ± 0.3 v.s.
9.97 ± 0.2 m.-s.
6.65 ± 0.1 w.
5.15 ± 0.08 w.
4.97 ± 0.06 w.-m.
4.70 ± 0.06 w.-m.
3.95 ± 0.05 w.
3.64 ± 0.04 w.-m.
3.53 ± 0.04 w.-m.
3.43 ± 0.03 s.
3.32 ± 0.03 m.
3.20 ± 0.03 m.
2.94 ± 0.02 w.
2.82 ± 0.02 w.
______________________________________
Claim 14
Dependent Claim
58 words
The method of claim 1 wherein the mixture provided for in step (A) is a gel, said gel being prepared by (i) providing a first mixture comprising a colloidal dispersion of silica, (ii) providing a second mixture comprising water, said organic dye and said mineralizing agent, and (iii) combining said first and second mixture to provide said gel.
Claim 15
Dependent Claim
34 words
The method of claim 1 wherein said organic dye is selected from the group consisting of the viologens, methyl green, ethyl green, methylene blue, methyl violet, methylene green, methyl violet 2B and alcian blue.
Claim 16
Dependent Claim
24 words
The method of claim 14 wherein said viologens are selected from the group consisting of methyl viologen, ethyl viologen, benzyl viologen and betaine viologen.
Claim 17
Dependent Claim
19 words
The method of claim 1 wherein R 1 , R 4 , R 5 and R 6 are methyl.
Claim 18
Dependent Claim
17 words
The method of claim 1 wherein R 2 and R 7 are independently hydrogen, methyl or ethyl.
Claim 19
Dependent Claim
13 words
The method of claim 1 wherein R 3 and R 8 are methyl.
Claim 20
Dependent Claim
17 words
The method of claim 1 wherein Q is a halide, phosphate, nitrate, carbonate, acetate, formate or butyrate.
Claim 21
Dependent Claim
51 words
The method of claim 1 wherein Q is represented by the formula EX 4 wherein E is selected from the group consisting of Al, Zn, Cd, Hg, Ga, Pd, Pt, Fe, Cr, Mn, Co or Ni, and X is selected from the group consisting of Cl, F, Br, I or CN.
Claim 22
Dependent Claim
16 words
The method of claim 1 wherein R 9 and R 10 are independently aliphatic or aromatic.
Claim 23
Dependent Claim
21 words
The method of claim 1 wherein R 9 and R 10 are alkyl groups of 1 to about 10 carbon atoms.
Claim 24
Dependent Claim
13 words
The method of claim 1 wherein R 9 and R 10 are benzyl.
Claim 25
Dependent Claim
14 words
The method of claim 1 wherein R 9 and R 10 are each methyl.
Claim 26
Dependent Claim
14 words
The method of claim 1 wherein said oxide of silicon source is silica sol.
Claim 27
Dependent Claim
17 words
The method of claim 1 wherein said mineralizing agent is an alkali or alkaline earth metal compound.
Claim 28
Dependent Claim
18 words
The method of claim 1 with the step of separating said silica molecular sieve from its mother liquor.
Claim 29
Dependent Claim
14 words
The method of claim 1 with the step of washing said silica molecular sieve.
Claim 30
Dependent Claim
37 words
The method of claim 1 with the step of cation exchanging said silica molecular sieve with an ammonium salt, mineral acid or a salt of a catalytically active metal to provide a cation exchanged silica molecular sieve.
Claim 31
Dependent Claim
24 words
The method of claim 29 with the step of heat treating said cation exchanged silica molecular sieve in an inert, oxidizing or reducing atmosphere.
Claim 32
Dependent Claim
22 words
The method of claim 1 with the step of heat treating said silica molecular sieve in an inert, oxidizing or reducing atmosphere.
Claim 33
Dependent Claim
38 words
The method of claim 31 with step of cation exchanging said heat treated silica molecular sieve with an ammonium salt, mineral acid, or a salt of a catalytically active metal to provide a cation exchanged silica molecular sieve.
Claim 34
Dependent Claim
24 words
The method of claim 32 with the step of heat treating said cation exchanged silica molecular sieve in an inert, oxidizing or reducing atmosphere.
Claim 35
Dependent Claim
29 words
The method of claim 1 wherein the mole ratio during step (A) of H 2 O to OH - is in the range of about 10 to about 1000.
Claim 36
Dependent Claim
25 words
The method of claim 1 wherein said mixture is maintained in an enclosed container under at least the vapor pressure of water during step (B).
Claim 37
Dependent Claim
23 words
The method of claim 1 wherein the temperature during step (B) is in the range of about 125° C. to about 200° C.
Claim 38
Dependent Claim
21 words
The method of claim 1 wherein the time period for step (B) is from about 4 hours to about 30 days.
Claim 39
Dependent Claim
20 words
The method of claim 1 wherein the time period for step (B) is from about one to about fifteen days.
References Cited (Backward Citations)
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1989-04-14 | 1989-10-14 | 1990-04-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1993-04-14 | 1993-10-14 | 1994-04-15 | $3760.00 | Window Closed / Lapsed |
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